Coating compositions for forming toner receptive coatings

ABSTRACT

The present invention provides coating composition for forming a toner receptive coating on a substrate containing a polymer comprising: (a) a N-vinyl amide monomer, (b) a vinyl acetate monomer, (c) a substituted or unsubstituted monomer comprising a cyclic ether, and (d) a solvent. The coating compositions may further comprise a (e) non-reactive hydrophobic monomer. The invention also provides substrates coated with the toner receptive coatings.

FIELD OF THE INVENTION

This invention provides coating compositions for forming toner receptivecoatings on a substrate. This invention also provides substrates coatedwith the toner receptive coatings. The coating compositions include areactive monomer comprising an acetoacetate moiety, and may furthercomprise a non-reactive hydrophobic monomer.

BACKGROUND OF THE INVENTION

Coating compositions for forming toner receptive coatings are successfulmethod for forming images on different substrates such as paper,polyester, vinyl, and canvas. However, printing onto substrates such asplastics, such as vinyl, polyester, and polyolefin has not attained theprint quality, integrity, and adhesion commonly observed for papersubstrates.

United States Patent Application Publications US 2007/0092666 and US2007/0092668 disclose coating compositions for forming ink jet-receptivecoatings on a substrate. United States Patent Application PublicationU.S. Pat. No. 8,198,353 B2 and U.S. Pat. No. 5,789,123 disclose coatingcompositions for forming liquid toner receptive coatings on a substrate.International Publication Number WO 2005/115763 A1 discloses coatingcompositions for forming liquid toner receptive coatings on a substrate.

WO 2012/051153 and WO 2012/148533 disclose lactamic polymers containingan acetoacetate moiety.

U.S. Pat. Nos. 5,798,426, 5,852,094, and 6,969,734 B1 discloseacetoacetate containing materials. International Publication Number WO2010/120278 A1 discloses latex polymer particles comprising theacetoacetate moiety. International Publication Number WO 2004/029118 A2discloses materials comprising the acetoacetate-functional donorcompounds. The reactive functionality of a polyvinyl amide polymerizablepolymer comprising an acetoacetate moiety is disclosed in “UV-coatingformulation in a new light: A new lactamic oligomer formulating tool toovercome current challenges” by D. K. Hood et. al. (European CoatingsJournal 1: p36-38, 2013).

The functional attributes of acetoacetoxyethyl methacrylate aredisclosed in Eastman Chemical's “Acetoacetoxyethyl methacrylate (AAEM)Acetoacetyl Chemistry” Brochure (Publication Number N-319C, December1999), which disclosure is incorporated by reference herein. Thefunctional and chemical attributes of diketene chemistry are disclosedin “Diketene” by R. Clemens (Chemical Reviews, Volume 86, Number 2,April 1986), which disclosure is incorporated by reference herein. Thefunctional and chemical attributes of ketene chemistry are disclosed in“Ketenes II” by T Tidwell (J. Wiley and Sons, New Jersey, USA, 2006),which disclosure is incorporated by reference herein.

EP 1578824B1 describes a curable liquid composition containing anacryloyl group containing resin produced by reacting monofunctionalvinyl compounds and multifunctional acrylic esters with β-dicarbonylgroup. Self-initiating photocurable resins that UV-cure with little orno photoinitiator are described in Michael L. Gould et al., NovelSelf-Initiating UV-Curable Resins: Generation Three, 1 PROCEEDINGS FROMRADTECH EUROPE 05, 245-51 (2005). These disclosures are incorporated byreference herein.

Accordingly, there is a need for improved toner receptive coatings,which exhibit improved properties including the ability to absorb andretain the ink effectively in both solvent-based and water-based inkprintable forms. There is also a need to provide substrates which arecoated with coating compositions that are both solvent-based andwater-based ink printable.

SUMMARY OF THE INVENTION

The present invention provides coating compositions for forming a tonerreceptive coating on a substrate containing a polymer comprising: (a) aN-vinyl amide monomer, (b) a vinyl acetate monomer, (c) a reactivemonomer comprising an acetoacetate moiety, and (d) a solvent. Thecoating compositions may further comprise (e) a non-reactive hydrophobicmonomer.

The present invention further provides toner substrates coated with thecoating compositions.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides coating compositions for forming toner receptivecoatings on a substrate. This invention also provides substrates coatedwith the toner receptive coatings. The coating compositions include areactive monomer comprising an acetoacetate moiety, and may furthercomprise a non-reactive hydrophobic monomer.

As used herein, the following terms have the meanings set out below.

The term “acidic conditions” refers to conditions relating to the pHvalue of an aqueous solution. Pure water is considered to be neutral,with a pH close to 7.0 at 25° C. Solutions with a pH value less than 7are considered to be acidic solutions.

The term “anion” refers to an “anionic” (adjective) ion, which has moreelectrons than protons, providing it with a net negative charge.

The term “anionic addition polymerization” refers to a form ofchain-growth polymerization or addition polymerization that involves thepolymerization of vinyl monomers with strong electronegative groups. Thepolymerization is carried out through a carbanion active species.Addition polymerizations take place in three steps: chain initiation,chain propagation, and chain termination.

The term “basic conditions” refers to conditions relating to the pHvalue. Pure water is considered to be neutral, with a pH close to 7.0 at25° C. Solutions with a pH value greater than 7 are considered to bebasic or alkaline.

The term “branched and unbranched alkyl groups” refers to alkyl groups,which may be straight chained or branched. For example, the alkyl groupshave from 1 to about 30 carbon atoms, more particularly, from 1 to about25 carbon atoms, and yet more particularly from 1 to about 20 carbonatoms. Branched groups include isopropyl, sec-butyl, tert-butyl, and thelike.

The term “cation” refers to an “cationic” (adjective) ion, which hasfewer electrons than protons, providing it with a net positive charge.

The term “copolymer” refers to chains comprising more than one type ofmonomer unit.

The term “cyclic” in chemistry refers to a compound in which a series ofatoms is connected to form a loop or ring. The vast majority of cycliccompounds are organic. Cyclic compounds may or may not be aromatic. Theterm “polycyclic” is used when more than one ring is formed in a singlemolecule.

The term “ether” refers to a class of organic compounds that contain anether group, an oxygen atom connected to two alkyl or aryl groups. Anexample is the solvent diethyl ether (CH₃CH₂OCH₂CH₃). Ethers are commonin organic chemistry and pervasive in biochemistry, as they are commonlinkages in carbohydrates and lignin.

The term “halogen” refers to chloro, bromo, iodo and fluoro, and in oneembodiment is bromo and/or chloro.

The term “heteroatom” refers to atoms such as oxygen, nitrogen, sulfur,and phosphorous. When the heteroatom is a nitrogen atom, the nitrogenatom may be present in the form of a quaternary amine.

The term “hydrophilic” refers to a molecular entity that tends to bepolarized and is attracted to, and tends to be dissolved by, water. Ahydrophilic molecule or portion of a molecule is one that has a tendencyto interact with or be dissolved by water and other polar substances. Ahydrophilic molecule or portion of a molecule is one that is typicallycharge-polarized and capable of hydrogen bonding, enabling it todissolve more readily in water than in oil or other hydrophobicsolvents.

The term “hydrophobic” refers to a molecular entity that tends to benon-polar and, thus, prefers other neutral molecules and non-polarsolvents. Examples of hydrophobic molecules include the alkanes, oils,fats, and greasy substances in general. Hydrophobic is often usedinterchangeably with lipophilic, “fat-loving”; however, the two termsare not synonymous.

The term “inert solvent” refers to a solvent that does not interferechemically with the reaction.

The term “mineral acid” refers to an acid derived from one or moreinorganic compounds. Mineral acids release hydrogen ions when dissolvedin water. Commonly used mineral acids are sulfuric acid, hydrochloricacid, and nitric acid.

The term “monomer” refers to the repeat units comprising a polymer. Amonomer is a small molecule that chemically bonds to other monomers toform a polymer.

The term “non-homopolymer” refers to a polymer formed from two or moremonomers and includes essentially all polymers that are nothomopolymers. Nonlimiting examples of non-homopolymers includecopolymers, terpolymers, tetramers, and the like, wherein thenon-homopolymer is a random, blocked, or alternating polymer.

The term “nonion” refers to an “nonionic” (adjective) ion, an ion thathas no charge.

The term “pH” refers to a measure of the acidity or basicity of anaqueous solution. Pure water is considered to be neutral, with a pHclose to 7.0 at 25° C. Solutions with a pH less than 7 are considered tobe acidic and solutions with a pH greater than 7 are considered to bebasic or alkaline.

The term “polymer” refers to a large molecule (macromolecule) composedof repeating structural units (monomers) connected by covalent chemicalbonds.

The term “polymerization” refers to methods for chemically reactingmonomer compounds to form polymer chains. The polymer chain may bealternating, branched, blocked, or random. The type of polymerizationmethod may be selected from a wide variety of methods. Such methodsinclude, but are not limited to, free radical polymerization methods,such as classical radical polymerization and controlled radicalpolymerization, Nitroxide Mediation Polymerization (NMP), Atom TransferRadical Polymerization (ATRP), and Reversible Addition FragmentationChain-Transfer (RAFT).

The term “reactive solvent” refers to a solvent capable of transforming,particularly polymerizing or curing, upon suitable activation orinitiation. Examples include monomers comprising at least one cyclicether or vinyl ether functional groups capable of solvating an inventivepolymer. Background on epoxy chemistry and technology can be found inthe “Handbook of Epoxy Resins” by Lee and Neville (McGraw-Hill, NewYork, 1967). Blends of reactive solvents and polymerizable polymers mayalso be employed.

The present invention provides coating compositions for forming a tonerreceptive coating on a substrate containing a polymer comprising: (a) aN-vinyl amide monomer, (b) a vinyl acetate monomer, (c) a reactivemonomer comprising an acetoacetate moiety, and (d) a solvent.

Preferably, the (a) N-vinyl amide monomer is selected from the groupconsisting of N-vinyl pyrrolidone, N-vinyl valerolactam, N-vinylcaprolactam, hydroxyethylpyrrolidone methacrylate, and N-vinylformamide. More preferably, the (a) N-vinyl amide monomer is selectedfrom the group consisting of N-vinyl pyrrolidone, N-vinyl valerolactam,and N-vinyl caprolactam.

Additional examples of suitable lactamic monomers (N-vinyl amidemonomers) are disclosed in “A novel route to substituted poly(vinylpyrrolidone)s via simple functionalization of 1-vinyl-2-pyrrolidone inthe 3-position by ring-opening reactions” by H. Reinecke et. al. (Eur.Poly. J., 46 (2010) p1557-1562) and “Synthesis and polymerization of newpyrrolidone-containing methacrylate monomers” by T. P. Davis et. al.(Polymer, 39, 17, p4165-4169, 1998). Background on the chemistry,structure, and properties of lactamic polymers can be found in “N-VinylAmide Polymers” by E. S. Barabas (Encyclopedia of Polymer Science andEngineering, 17, 2^(nd) ed., p 198-257, (1989)) and in “Polymers ofN-Vinylpyrrolidone: Synthesis, Characterization and Uses” by F. Haaf, A.Sanner, and F. Straub (Polymer Journal, 17, 1, p143-152 (1985)).

The (b) vinyl acetate (ethenyl acetate, ethenyl ethanoate) monomer is anorganic compound derived from the formula CH₃COOCH═CH₂.

Preferably, the combination of the (a) N-vinyl amide monomer, the (b)vinyl acetate monomer is selected from the group consisting ofpoly(N-vinyl pyrrolidone-co-vinyl acetate) materials including PVP/VAE-335, 1-335, E-535, 1-535, E-735, and 1-735, available from AshlandSpecialties Ingredients. Examples of poly(N-vinyl pyrrolidone-co-vinylacetate) also include Luvitec VA 64, VA 64W and the hydrophobicallymodified Collacral® VAL, available from BASF. Collacral® VAL is anaqueous solution of a vinylpyrrolidone copolymer used to thicken andstabilize polymer dispersions and other aqueous systems. Collacral® VALis employed as a thickener for polymer dispersions and other aqueoussystems and can be used as a protective colloid when resin solutions aremixed with polymer dispersions. Collacral® VAL has a maximum thickeningeffect in polymer dispersions at a pH of approximately 5. Collacral® VALcan also be employed as a protective colloid in the production of resindispersions and when resin solutions are mixed with polymer dispersions.More preferably the combination polymer is N-vinyl pyrrolidone-co-vinylacetate include PVP/VA E-535, 1-535, W-635, S-630, and E-635, availablefrom Ashland Specialties Ingredients.

The monomer in the (c) reactive monomer comprising an acetoacetatemoiety may be selected from the group consisting of amide, alkyl,carboxyl, carbonyl, and ether groups. The (c) reactive monomercomprising an acetoacetate moiety may be selected from the groupconsisting of acetoacetoxyethyl methacrylate, acetoacetoxyethylacrylate, and allyl acetoacetate.

Suitable (d) solvents in the coating compositions comprise aqueous andnon-aqueous solvents. Illustrative non-limiting examples of solventsinclude water, ethanol, isopropanol, butanol, acetone, methyl ethylketone, ethyl acetate, reactive solvents and mixtures thereof. Othersuitable solvents are described in the “Industrial Solvents Handbook,4^(th) Edition” edited by E. W. Flick (Noyes Data Corporation, ParkRidge, N.J., 1991) and in the “Polymer Handbook, 4^(th) Edition,” editedby J. Brandrup et. al. (J. Wiley and Sons, New York, 1999), whichdisclosures are incorporated by reference herein. A solvent is asubstance that dissolves a solute resulting in a solution. In solution,all of the ingredients are uniformly distributed at a molecular leveland no residue remains. The mixing is referred to as miscibility,whereas the ability to dissolve one compound into another is known assolubility. However, in addition to mixing, both substances in thesolution interact with each other. Solvents can be broadly classifiedinto two categories: polar and non-polar. The polarity, dipole moment,polarizability and hydrogen bonding of a solvent determines what type ofcompounds it is able to dissolve and with what other solvents or liquidcompounds it is miscible. Polar solvents dissolve polar compounds bestand non-polar solvents dissolve non-polar compounds best. Strongly polarcompounds like sugars (e.g., sucrose) or ionic compounds, like inorganicsalts (e.g., table salt) dissolve only in very polar solvents likewater, while strongly non-polar compounds like oils or waxes dissolveonly in very non-polar organic solvents like hexane. Similarly, waterand hexane (or vinegar and vegetable oil) are not miscible with eachother.

Examples of reactive solvents and co-solvents include, but are notlimited to, 2-hydroxy methyl methacrylate (HEMA), 2-hydroxy ethylacrylate (HEA), 2-phenoxy ethyl acrylate (PEA), 2-ethylhexyl-diglycolacrylate, 2-(2-ethoxyethoxy)ethyl acrylate (EOEOEA), lauryl acrylate(LA), stearyl acrylate (SA), isobornyl acrylate (IBOA), acrylicacid-2-ethylhexyl ester, isodecyl acrylate, diacetone acrylamide,acryloyl morpholine (ACMO), cyclic trimethylol-propane formal acrylate(CTFA), 3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC),4-hydroxybutyl acrylate, (3-Acrylamidopropyl)trimethylammonium chloride(APTAC), C8-C 10 acrylate (ODA), isodecyl acrylate (ISODA), laurylmethacrylate (LM), stearyl methacrylate (SM), 2,2,2-trifluoroethylmethacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid,2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt,[2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide,[3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxideinner salt, 1,6-hexanediol diacrylate (HDDA), dipropylene glycoldiacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), water,alcohol, hydro-alcohol mixtures, 1,4-butanediol diacrylate (BDDA),tripropylene glycol diacrylate (TPGDA), dipropyleneglycol diacrylate(DPGDA), tripropylene glycol diacrylate (TRPGDA), 1,9-nonanedioldiacrylate (NNDA), neopentyl glycol diacrylate (NPGDA), propoxylatedneopentyl glycol diacrylate (NPG2PODA), polyethylene glycol (200)diacrylate (PEG(200)DA), polyethylene glycol (400) diacrylate(PEG(400)DA), polyethylene glycol (600) diacrylate (PEG(600)DA),ethoxylated bisphenol-A diacrylate (BPA2EODA), triethylene glycoldiacrylate (TEGDA), triethylene glycol dimethacrylate (TEGDMA), glycerolpropoxylated triacrylate (GPTA), diethylene glycol dimethacrylate(DEGDMA), ethoxylated bisphenol-A dimethacrylate (BPA10EODMA),trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate(PET3A), ethoxylated tri-methylolpropane triacrylate (TMP3EOTA),propxylated tri-methylolpropane triacrylate (TMP3POTA), propoxylatedglyceryl triacrylate (GPTA), trimethylolpropane trimethylacrylate(TMPTMA), ethoxylated trimethylolpropane trimethacrylate (TMP3EOTMA),2,2-dionol diacrylate, pentaerythritol tetraacrylate (PETA),neopentylglycol diacrylate hydroxypivalate, 2-acryloyloxyethylphthalicacid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid,dimethyloltricyclodecane diacrylate, 2-acryloyloxyethylsuccinic acid,nonylphenol ethylene oxide adduct acrylate, phenol acrylates,methoxy-polyethylene glycol acrylate, tetramethylolmethane triacrylate,dipentaerythritol hexaacrylate (DPHA), isocyanate-functional unsaturatedacrylic ester resin, urethane diacrylates oligomers, urethane acrylates,modified urethane acrylates, polyester acrylates, modified bisphenol Adiacrylate, phenoxy-polyethylene glycol acrylate, bisphenol A propyleneoxide modified diacrylate, bisphenol A ethylene oxide adduct diacrylate,pentaerythritol triacrylate hexamethylenediisocyanate, urethaneprepolymer, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate,carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate,glycidyl acrylates, acrylamides, polyfunctional acrylamides,polyfunctional (polyethylene glycol) acrylates, polyfunctional vinylamides, 1,4-butane-diol-monoacrylate and/or diglycidyl ether of1,4-butanediol, and the like, and mixtures thereof.

Additional examples of reactive solvents and co-solvents include, butare not limited to, methyl vinylether, ethyl vinylether, propylvinylether, n-butyl vinylether, t-butyl vinylether, 2-ethylhexylvinylether, n-nonyl vinylether, lauryl vinylether, cyclohexylvinylether, cyclohexylmethyl vinylether, 4-methylcyclohexylmethylvinylether, benzyl vinylether, dicyclopentenyl vinylether,2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinylether,ethoxyethyl vinylether, butoxyethyl vinyl ether, methoxyethoxyvinylether, ethoxyethoxyethyl vinylether, methoxypolyethylene glycolvinylether, tetrahydrofurfuryl vinylether, dodecyl vinylether,diethylene glycol monovinylether, 2-hydroxyethyl vinylether,2-hydroxypropyl vinylether, 4-hydroxybutyl vinylether,4-hydroxymethylcyclohexylmethyl vinylether, polyethylene glycolvinylether, chloroethyl vinylether, chlorobutyl vinylether, phenylethylvinylether, phenoxypolyethylene glycol vinylether, ethylene glycoldivinylether, butylenes glycol divinylether, hexandiol divinylether,bisphenol A alkyleneoxide divinylethers, bisphenol F alkyleneoxidedivinylethers, propyleneoxide adducts of trimethylolpropanetrivinylether, triethylene glycol divinylether, cyclohexane dimethanoldivinylether, N-vinyl-2-pyrrolidone (VP), N-vinyl caprolactam (VCap),N-vinyl imidazole (VI), n-vinyl amides, 4-vinyl pyridine, 2-vinylpyridine, styrene, 5-vinyl-2-norbornene and the like, and mixturesthereof.

Preferably, (a) is 0.1-80%, (b) is 1-80%, (c) is 0.1-80%, and (d) is to100%, by weight. More preferably, (a) is 1-70%, (b) is 1-60%, (c) is0.5-20%, and (d) is to 100%, by weight. Most preferably, (a) is 1-60%,(b) is 1-50%, (c) is 0.1-10%, and (d) is to 100%, by weight.

Preferably, the polymer comprising: (a) a N-vinyl amide monomer, (b) avinyl acetate monomer, (c) a reactive monomer comprising an acetoacetatemoiety, and (d) a solvent is selected from the group consisting of vinylpyrrolidone/vinyl acetate/acetoacetoxyethyl methacrylate, vinylcaprolactam/vinyl acetate/acetoacetoxyethyl methacrylate, vinylpyrrolidone/vinyl acetate/allyl acetoacetate, and vinylcaprolactam/vinyl acetate/allyl acetoacetate.

In another aspect, the polymer further comprises (e) a non-reactivehydrophobic monomer. The (e) non-reactive hydrophobic monomer maycomprise a non-reactive C₁-C₂₀ alkyl acrylate monomer. Preferably, the(e) non-reactive C₁-C₂₀ alkyl acrylate monomer is selected from thegroup consisting of stearyl acrylate, butyl acrylate, octyl acrylate,decyl acrylate, and lauryl (meth)acrylate.

Preferably, the polymer comprising: (a) a N-vinyl amide monomer, (b) avinyl acetate monomer, (c) a reactive monomer comprising an acetoacetatemoiety, and (e) an additional hydrophobic monomer moiety is selectedfrom the group consisting of vinyl caprolactam/vinylacetate/acetoacetoxyethyl methacrylate/stearyl acrylate, and vinylcaprolactam/vinyl acetate/allyl acetoacetoacetate/stearyl acrylate.

Polymers in accordance with the present invention may be non-ionic,anionic, or cationic. Furthermore, polymers or compositions containingthe polymers may be in powder, solid, liquid, or solution form.Compositions comprising the polymer may be curable via ultra violet (UV)radiation, thermal, electron beam, or gamma irradiation. The polymersmay be utilized in the formulation of aqueous, UV curable coatings, orin 100% solid, UV curable coatings. Compositions comprising the polymermay be thermally and/or cationically curable or thermally and/oranionically curable. The polymers or compositions containing thepolymers may be thermoplastic polymers that can be produced in eitherliquid or powder form.

Preferably, the polymer has a solids content of about 15-50% and aviscosity of about 200-15,000 cps. The composition may also be in theform of an aqueous dispersion. The coating composition has a polymersolids content of about 15-50% and a viscosity of about 200-3,000 cps.

The toner receptive coatings may be in the form of a liquid, solid, orwax. Preferably, the toner receptive coatings are in the form of aliquid

In another aspect, the invention provides a toner substrate coated witha coating composition containing a polymer comprising: (a) a N-vinylamide monomer, (b) a vinyl acetate monomer, and (c) a reactive monomercomprising an acetoacetate moiety.

In another aspect, the invention provides a flexible food packagesubstrate coated with a coating composition containing a polymercomprising: (a) a N-vinyl amide monomer, (b) a vinyl acetate monomer,(c) a reactive monomer comprising an acetoacetate moiety, and (e) anadditional hydrophobic monomer moiety.

The present invention further provides toner substrates coated with thecoating compositions.

Polymeric binders, also referred to as emulsions, latexes, adhesives,glues, dispersions, or resins, are versatile systems in the constructionand design of polymers. Examples of suitable binder classes includestyrene butadiene rubber (SBR) latex, styrene acrylate, polyvinylalcohol and copolymers, polyvinyl acetate copolymers, vinyl acetatecopolymers, carboxylated SBR latex, polyolefins and copolymer ofpolyolefins (i.e.; poly(ethylene-co-acrylic acid) andpoly(ethylene-co-vinyl acetate)), styrene acrylate copolymers,styrene/butadiene/acrylonitrile,styrene/butadiene/acrylate/acrylonitrile, polyalkylene imines, polyvinylpyrrolidone and copolymers, polyurethanes, polyamines, polyamides,cationic polyurethanes, polyethylene oxide, poly(2-ethyl-2-oxazoline),polyester resins, gelatins, casein, alginate, cellulose derivatives,hydroxyethyl cellulose, ethyl cellulose, hydroxypropyl cellulose,starches, ethoxylated, oxidized and enzyme converted starches, cationicstarches, guar, cationic guar, water soluble gums, acrylic vinylpolymers, soy protein polymers as well as mixtures of water soluble andwater-insoluble resins, latexes may be used. Latex binders are mostcommonly emulsions (polymer particles suspended in a liquid medium).

Preferably, a binder is present in the coating compositions of theinvention. A preferred binder is a vinyl acetate-ethylene copolymer,such as Vinnapas® 465 Emulsion, available from Wacker Chemie, AG.Vinnapas® 465 Emulsion is a rapid-setting vinyl acetate-ethylenecopolymer, which is a high-solids emulsion. This polymer adheres well tovarious substrates such as polyester, poly(ethylene terephthalate),tempered aluminum foil and polystyrene. This emulsion combines ahigh-solids content with a low viscosity, which is a combination thatpermits the addition of high-filler loadings, resulting in adhesiveformulations with solid contents of 80%, or more. Furthermore, thisemulsion does not thicken excessively on the addition of plasticizers,which allows for the formulation of very high-solids adhesives.Vinnapas® 465 Emulsion also is shear stable, and can be applied onhigh-speed packaging machines using roll, extrusion, or spray equipment.The emulsion dries to a slightly tacky, clear, water-resistant film.Another preferred binder is Witcobond W-213 polyurethane dispersion,available from Uniroyal Chemical. Witcobond W-213 polyurethanedispersion is a waterborne, cationic dispersion from aliphaticurethanes. Strong, cohesive films can be produced simply by theevaporation of its water content. Witcobond W-213 polyurethanedispersion is used with cationic additives as a protective coating orsurface treatment, where the properties of a light stable, waterborneurethane are suitable, primarily for textiles, nonwovens, fiberglass,paper, wood, urethane foam, or other porous substrates.

Preferably a pigment or pigments (colorant or colorants) are used in thecoating compositions of the invention. Suitable pigment materials aredescribed in Hunger's “Industrial Organic Pigments,” Itoh's “Dictionaryof Pigments,” and Leach and Pierce's “Printing Ink Manual.” Pigment canbe added by mixing components. Pigment or pigments may be added with aplasticizer and/or a filler. The exact choice and amount of pigment willdepend upon the final desired coating composition and such informationis well known in the art.

The electrophotographic process is disclosed in “Effect of Toner FixingTemperature on Print Properties in the Electrophotographic Process” byT. Hartus (TAGA Journal, 4, 2008, 165-177). The adhesion science oftoner is disclosed in “Adhesion of Electrophotographic Toner on Paper”by T. Hartus (Graphic Arts in Finland 30, 2001, 3). Information relatedto the electrophotographic process as well as liquid and dry tonermaterials can be found in “Handbook of Imaging Materials” by A. S.Diamond and D. S. Weiss (ed.) (Marcel Dekker, 2002). Preferably, thetoner receptive coating is suitable for fusing to toner at temperaturesbetween 50° C. and 175° C.

Preferably a surfactant is used in the coating compositions of theinvention. Surfactants (wetting agents, are compounds that lower thesurface tension of a liquid, the interfacial tension between twoliquids, or that between a liquid and a solid. Surfactants may act asdetergents, emulsifiers, foaming agents, and dispersants. Surfactantsare usually organic compounds that are amphiphilic, meaning they containboth hydrophobic groups and hydrophilic groups. Therefore, a surfactantcontains both a water-insoluble (or oil-soluble) component and awater-soluble component. Surfactants will diffuse in water and adsorb atinterfaces between air and water or at the interface between oil andwater, in the case where water is mixed with oil. The insolublehydrophobic group may extend out of the bulk water phase, into the airor into the oil phase, while the water-soluble head group remains in thewater phase. This alignment of surfactants at the surface modifies thesurface properties of water at the water/air or water/oil interface. Theexact choice and amount of surfactant will depend upon the final desiredcoating composition and such information is well known in the art.

Other suitable components for aqueous based coatings of this inventioninclude silicates and silica gels, free radical initiators, aluminatesand aluminas, N-vinyl-2-pyrrolidone, N-vinyl-caprolactam, other N-vinylamides, 1-vinyl imidazole, 4-acryloyl morpholine, polyvinyl pyrrolidone,polyvinyl alcohol, acetoacetylated polyvinyl alcohol, oxygen scavengers,styrene/acrylate latexes, acrylic latexes, polyalkylene glycols, maleicanhydride-co-methyl vinyl ether polymers, polyalkylene imines, oxetanes,oxazolines, benzoxazines, polydi allyldialkylammonium chloridematerials, starch, acrylated epoxides, glycidyl acrylate monomers,polyurethanes, acrylated oligomers of polyurethanes, acrylated glycidyloligomers, polyfunctional acrylates, polyfunctional aziridines, clays,calcium carbonates, talcs, cellulosics, cycloaliphatic epoxides, vinylethers, epoxy based dispersions, anionic surfactants (i.e., sodiumlauryl sulfate), non-ionic surfactants, cationic surfactants, silanes orsilicone based polymers, and anionic polyacrylates, such as polyacrylicacid. Optional components in the composition for optimization of thecoating composition when coated on different substrates includepigments, clays, e.g. organoclays and water-swellable clays, acrylicpolymers, acrylic copolymers, alginates, carrageenan, microcrystallinecellulose, gelatin, carboxymethylcellulose sodium,hydroxyethylcellulose, hydroxypropylcellulose,hydroxypropylmethylcellulose, methylcellulose, guar and guarderivatives, locust bean gum, polyethylene oxide, polyvinylpyrrolidones,copolymers of polyvinylpyrrolidones, polyvinylalcohols, charge controlagents, optical brighteners, other water soluble polymers, silicas,aluminates, zirconates, calcium carbonates, xanthan gums, polymers orcopolymers of water soluble vinyl lactams optionally having insitu-formed particles of crosslinked vinyl lactam polymers orcopolymers, crosslinked polyvinyl pyrrolidone, and crosslinkers toachieve advantageous printable surface coatings having light stability(see U.S. Pat. No. 6,872,787 B2). Preferred components and optimalamounts of these components will depend upon the specific supportcoating and application and can be readily determined by one of ordinaryskill in the art.

The present invention relates to curing or cross-linking or polymerizinga polymerizable material carried out by any appropriate method known inthe arts. Insight into curing and cross-linking technology is disclosedin “Thermosetting Polymers,” J. P. Pascault et. al. (Marcel Dekker, NewYork, 2002), which disclosure is incorporated by reference herein. Thepolymerization of reactive solution comprising polymerizable polymer maybe carried out by employing any of the methods disclosed in “Principlesof Polymerization 4^(th) edition,” by George Odian (J. Wiley and Sons,Hoboken, N.J., 2004), which disclosure is incorporated by referenceherein. The preferable techniques or methods employed by the presentinvention to polymerize the polymers would include UV-radiation, UV-LED,laser beam, electron beam, gamma irradiation, free-radical, cationic,anionic, thermal, exposure to e-beam and/or by employing a high-energysource in presence of suitable photo initiator for the initiation ofpolymerization. Suitable sources of radiation include, but are notlimited to, mercury, xenon, halogen, carbon arc lamps, sunlight, andradioactive sources.

In order to induce polymerization via irradiation, photoinitiators areoften incorporated to initiate the polymerization reaction system.Preferable photoinitiators are selected from the following non-limitinggroup or class of compounds such as2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenylketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morphorinopropane-1-one;benzoins e.g. benzyl dimethyl ketal; benzophenones such as benzophenone,4-phenylbenzophenone, and hydroxybenzophenone; thioxanthones such asisopropylthioxanthone and 2,4-diethylthioxanthone; acylphosphine oxides;and other special initiators such as methyl phenyl glyoxylate;bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)phenyl sulfide], a mixtureof bis [4-diphenylsulfonio]phenyl)sulfide bis(hexafluoroantimonate anddiphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate,bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)phenyl sulfide],5-2,4-cyclopentadiene-1-yl-[1,2,3,4,5,6-.eta.)-(1-methylethyl-)benzene]-iron(1+)-hexafluorophosphate(1−)),4-(2-hydroxytetradecanyloxy)diphenyliodonium hexafluoroantimonate,(4-hydroxynaphtyl)dimethylsulfonium hexafluoroantimonate), photo latentbases such as photo latent diazabicyclo nonene, triphenylsulfoniumhexafluorophosphate, triphenylsulfonium hexafluoroantimonate,4-methoxyphenyldiphenylsulfonium hexafluoroantimonate,4-methoxyphenyliodonium hexafluoroantimonate,bis(4-tert-butylphenyl)iodonium tetrafluoroborate,(bis(4-tert-butylphenyl)iodonium hexafluorophosphate),(bis(4-tert-phenyl)iodonium hexafluoroantimonate), (bis[4-(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate)),aryldiazonium salts, diaryliodonium salts, triaylsulfonium salts,triarylselenonium salts, dialkylphenacylsulfonium salts,triarylsulfoxonium salts, triethanol amine, aryloxydiarylsulfoniumsalts, and the like for example, triphenylsulfonium hexaflurophosphate,methyidiphenylsulfonium hexafluorophosphate, dimethylphenylsulfoniumhexaflurophosphate, diphenyinapththylsulfonium hexaflurophosphate,di(methoxynapththyl)methylsulfonium hexaflurophosphate,(4-octyloxyphenyl)phenyl iodonium hexafluoro antimonate,(4-octyloxyphenyl)diphenyl sulfonium hexafluoro antimonate,(4-decyloxyphenyl)phenyl iodonium hexafluoro antimonite,(4-dodecyloxyphenyl)diphenyl sulfonium hexafluoroantimonate. Preferably,the photoinitiator includes10-biphenyl-4-yl-2-isopropyl-9H-thixanthen-10-ium hexafurophosphate,4,4′-dimethyl iodonium hexaflurophosphate, mixed triarylsulfoniumhexaflurophosphate salts and reaction products of polyol and10-(2-carboxymethoxy)-biphenyl-4yl-2-isopropyl-9-oxo-9H-thioxanthen-10-iumhexafluorophosphate. The photoinitiators may be used alone or incombinations thereof. Alternatively, the photoinitiator may be used bymixing it with one or more photopolymerization accelerator, such as abenzoic acid (e.g., 4-dimethylaminobenzoic acid) or a tertiary amine(e.g., diazabicyclo nonene (DBN)), in any appropriate ratio. Thephotoinitiator is preferably added to the photopolymerizable compositionin the range of about 0.1% to about 20% by weight.

The coating compositions of the invention can provide a glossy,transparent to matte, opaque finish coating on synthetic films such aspolyester, vinyl, polyolefins, and the like, as well as paper andcanvas.

Generally, the coating composition has a solids content of about asolids content of about 15-50% and a viscosity of about 200-3000 cps.

The polymer in the coating composition suitably has a K-Value of about 5to about 100, preferably about 10 to about 70.

Colloidal silica, amorphous colloidal silica particles may be included,e.g. 20-150 n. Preferred colloidal silicas are Silcron IJ-25 and IJ-50.Silica gels, amorphous colloidal silica particles, may also be included,e.g., 4-7 microns. A preferred silica gel is Silcron G 100.

The polymers of the present invention are suitable for use inindustrial, personal care, household, and pharmaceutical applications.Industrial uses include, but are not limited to, formulating inks,flocculation agents, hydrogels, surface modification agents, coatings,microporous print media, paper sizing additives, shale swell inhibitors,metal coatings, metal working fluids, rheology modifiers, reactivebiocides, decorated titanium, interlaminate adhesives, agriculturalcompositions, dispersants, batteries, products comprised of iodine,products comprised of silver, products comprised of carbon, productscomprised of nano carbons, comb/branch polymer adducts, biocidal films,tackifiers, latex weather resistant modifiers, decorated pigments forinks and pastes, decorated cenospheres, decorated barium sulfate,cross-linkers, automotive products and protective films, super-absorbers(i.e., diapers) (see U.S. Pat. App. 2009/0043005A1, the contents ofwhich are hereby incorporated by reference), printing plates,macro-initiating materials, products comprised of graphene, hydrophilicenhancement agents for membranes (see U.S. Pat. App. Ser. No. 61/242,900and PCT/US/2010/028852, the contents of which are hereby incorporated byreference), anti-fog coatings, polymer blocks, additives to extrudablecompounds and films, protective colloidal agents, multi dimensionalprinting materials including pigments, polymers and inks (for examplesee WO/2008/077850A2, the contents of which are hereby incorporated byreference), refractive index modifiers, cross-linking agents,microencapsulation particles and additives (see U.S. Pat. No. 5,811,121and WO 2007/146722 A1), rheology control agents, grease resistant paperand films, fiber sizing agents, products comprised of alumina,conductive films, cementitious compositions, bioadhesives, tabletcoatings, battery binders, resinous UV absorbers (U.S. patentapplication Ser. No. 12/698,583, the contents of which are herebyincorporated by reference), iodine stabilizers, conductive coatings andgels, reactive rheology modifying agents, macro-initiators, coating flexagents, and non-migratory anti-static agents. Personal care andhousehold applications include, but are not limited to, formulatingcosmetics, hair care products, toiletries, hydrogels, laundry productsand household cleaning products, and dye absorbent non-woven swatches.Pharmaceutical applications include, but are not limited to, processingaids, medical stents, lubricity modification agents, catheters and othermedical device coatings, active ingredient solubilizers, optical lenses,formulating drug delivery systems, and preparing tablet coatings.

The coating compositions can be prepared according to the examples setout below. The examples are presented for purposes of demonstrating, butnot limiting, the preparation of the coating compositions of thisinvention.

EXAMPLES

The following non-limiting examples are provided to illustrate a few ofthe methods for preparing novel coating compositions for forming tonerreceptive coatings. The examples are presented for purposes ofdemonstrating, but not limiting, the preparation of the compounds andcompositions of this invention.

Example 1 Synthesis of Vp/VA/AcAc (58.5/40/1.5)

Feed one is prepared with 58.37 g vinyl pyrrolidone (Vp), 2.88 gAcetoacetoxyethyl methacrylate (AcAc) and 46.04 g Isopropanol. Put172.65 g Isopropanol and 30.92 g Vinyl Acetate (VA) into the reactor andcommence purging of the reaction vessel with nitrogen. Heat the reactionflask containing Isopropanol to reflux ˜78° C. In a separate vesselprepare a mixture of Triganox 25C 75 (0.5 g) and Isopropanol (23 g).Label this vessel “Triganox Solution”. When the reaction flask hasreached reflux temperature, begin adding Feed 1, drop-wise, in to thereaction vessel over a period of 180 minutes. After 15 minutes ofmonomer feed, add 3 g of the Triganox Solution into the reactor.Continue the drop-wise addition of Feed 1 over a period of approximately165 minutes. While the monomers are feeding into the reactor, after 30minutes charge 3.0 g of the Triganox solution. After 45, 60, 75, 90, 105and 120 minutes, charge 3.0 g Triganox solution into the reactor. After150 minutes, charge 3.0 g Triganox solution into the reactor. At thecompletion of the monomer feeds, charge the reaction vessel with theremainder of the Triganox solution. The reaction vessel is allowed toheat at reflux for an additional 180 minutes. Note: during the initiatorshots, additional Isopropanol was added to replace any that hasvolatilized. Cool the reaction vessel and leave the material in thereactor. This is the end of ‘day one’. On ‘day two’, re-heat the vesselto reflux and charge with 2.0 g Triganox 25C 75. Hold for 2 hours. Addan additional 2.0 g Triganox 25C 75. Hold for 5 hours then cool reactionmixture.

Example 2 Synthesis of Vp/VA/AcAc (55/40/5)

Feed one is prepared with 54.38 g vinyl pyrrolidone (Vp), 9.53 gAcetoacetoxyethyl Methacrylate (AcAc) and 45.62 g Acetone. Put 171.07 gAcetone and 30.63 g and Vinyl Acetate (VA) into the reactor and commencepurging of the reaction vessel with nitrogen. Heat the reaction flaskcontaining Acetone to reflux ˜58° C. In a separate vessel prepare amixture of Triganox 25C 75 (0.5 g) and Acetone (23 g). Label this vessel“Triganox Solution”. When the reaction flask has reached refluxtemperature, begin adding Feed 1, drop-wise, in to the reaction vesselover a period of 180 minutes. After 15 minutes of monomer feed, add 2.25g of the Triganox Solution into the reactor. Continue the drop-wiseaddition of Feed 1 over a period of approximately 165 minutes. While themonomers are feeding into the reactor, after 30 minutes charge 2.25 ofthe Triganox solution. After 45, 60, 75, 90, 105 and 120 minutes, charge2.25 g Triganox solution into the reactor. After 150 minutes, charge 3.0g Triganox solution into the reactor. At the completion of the monomerfeeds, charge the reaction vessel with the remainder of the Triganoxsolution. The reaction vessel is allowed to heat at reflux for anadditional 180 minutes. Note: during the initiator shots, additionalAcetone was added to replace any that has volatilized. Cool the reactionvessel and leave the material in the reactor. This is the end of ‘dayone’. On ‘day two’, re-heat the vessel to reflux and charge with 2.0 gTriganox 25C 75. Hold for 2 hours. Add an additional 2.0 g Triganox 25C75. Hold for 5 hours then cool reaction mixture.

Example 3 Synthesis of VCap/VA/AcAc (58.5/40/1.5)

Feed one is prepared with 70.07 g vinyl caprolactam (VCap), 2.77 gAcetoactoxyethyl Methacrylate (AcAc) and 44.19 g Isopropanol. Put 165.72g Isopropanol and 29.68 g Vinyl Acetate (VA) into the reactor andcommence purging of the reaction vessel with nitrogen. Heat the reactionflask containing Isopropanol to reflux ˜78° C. In a separate vesselprepare a mixture of Triganox 25C 75 (0.5 g) and Isopropanol (22 g).Label this vessel “Triganox Solution”. When the reaction flask hasreached reflux temperature, begin adding Feed 1, drop-wise, in to thereaction vessel over a period of 180 minutes. After 15 minutes ofmonomer feed, add 3 g of the Triganox Solution into the reactor.Continue the drop-wise addition of Feed 1 over a period of approximately165 minutes. While the monomers are feeding into the reactor, after 30minutes charge 2.25 of the Triganox solution. After 45, 60, 75, 90, 105and 120 minutes, charge 2.25 g Triganox solution into the reactor. After150 minutes, charge 2.25 g Triganox solution into the reactor. At thecompletion of the monomer feeds, charge the reaction vessel with theremainder of the Triganox solution. The reaction vessel is allowed toheat at reflux for an additional 180 minutes. Note: during the initiatorshots, additional Isopropanol was added to replace any that hasvolatilized. Cool the reaction vessel and leave the material in thereactor. This is the end of ‘day one’. On ‘day two’, re-heat the vesselto reflux and charge with 2.0 g Triganox 25C 75. Hold for 2 hours. Addan additional 2.0 g Triganox 25C 75. Hold for 5 hours then cool reactionmixture.

Example 4 Synthesis of VCap/VA/AcAc (55/40/5)

Feed one is prepared with 65.46 g vinyl caprolactam (VCap), 9.17 gAcetoacetoxyethyl Methacrylate (AcAc) and 44.00 g Acetone. Put 164.66 gAcetone and 29.48 g Vinyl Acetate (VA) and into the reactor and commencepurging of the reaction vessel with nitrogen. Heat the reaction flaskcontaining Acetone to reflux ˜78° C. In a separate vessel prepare amixture of Triganox 25C 75 (0.5 g) and Acetone (22 g). Label this vessel“Triganox Solution”. When the reaction flask has reached refluxtemperature, begin adding Feed 1, drop-wise, in to the reaction vesselover a period of 180 minutes. After 15 minutes of monomer feed, add 3 gof the Triganox Solution into the reactor. Continue the drop-wiseaddition of Feed 1 over a period of approximately 165 minutes. While themonomers are feeding into the reactor, after 30 minutes charge 2.25 ofthe Triganox solution. After 45, 60, 75, 90, 105 and 120 minutes, charge2.25 g Triganox solution into the reactor. After 150 minutes, charge2.25 g Triganox solution into the reactor. At the completion of themonomer feeds, charge the reaction vessel with the remainder of theTriganox solution. The reaction vessel is allowed to heat at reflux foran additional 180 minutes. Note: during the initiator shots, additionalAcetone was added to replace any that has volatilized. Cool the reactionvessel and leave the material in the reactor. This is the end of ‘dayone’. On ‘day two’, re-heat the vessel to reflux and charge with 2.0 gTriganox 25C 75. Hold for 2 hours. Add an additional 2.0 g Triganox 25C75. Hold for 5 hours then cool reaction mixture.

Example 5 Synthesis of VCap/VA/AcAc/Stearyl Acrylate (45/40/5/10)

Feed one is prepared with 51.23 g vinyl caprolactam (VCap); 26.59 gStearyl Acrylate, 8.77 g Acetoacetoxyethyl methacrylate (AcAc) and 42.45g MEK. Put 157.51 MEK, and 28.20 g Vinyl Acetate (VA) into the reactorand commence purging of the reaction vessel with nitrogen. Heat thereaction flask containing Acetone to reflux—approximately ˜58C. In aseparate vessel prepare a mixture of Triganox 25C 75 (0.5 g) and MEK (21g). Label this vessel “Triganox Solution”. When the reaction flask hasreached reflux temperature, begin adding Feed 1, drop-wise, in to thereaction vessel over a period of 180 minutes. After 15 minutes ofmonomer feed, add 3 g of the Triganox Solution into the reactor.Continue the drop-wise addition of Feed 1 over a period of approximately165 minutes. While the monomers are feeding into the reactor, after 30minutes charge 2.3of the Triganox solution. After 45, 60, 75, 90, 105and 120 minutes, charge 2.3 g Triganox solution into the reactor. After150 minutes, charge 3.0 g Triganox solution into the reactor. At thecompletion of the monomer feeds, charge the reaction vessel with theremainder of the Triganox solution. The reaction vessel is allowed toheat at reflux for an additional 180 minutes. Note: during the initiatorshots, additional MEK was added to replace any that has volatilized.Cool the reaction vessel and leave the material in the reactor. This isthe end of ‘day one’. On ‘day two’, re-heat the vessel to reflux andcharge with 2.0 g Triganox 25C 75. Hold for 2 hours. Add an additional2.0 g Triganox 25C 75. Hold for 5 hours then cool reaction mixture.

Example 6 Ink Adhesion on Primer-Coated Clear Polyester TestingProcedure Method 1 Preparation of Ink Film and Ink Strips

HP Electroink Black was transferred entirely to a plastic container.This ink was folded repeatedly with a spatula by mixing the suspendedink particulates to a homogeneous ink paste.

The ink paste mentioned (20.0 g) and HP Imaging oil (10.0 g) were addedto a 60 ml screw-capped glass vial and mixed well by vigorous shaking toobtain a sample of diluted ink suspension.

Non-Corona treated surface of Clear Polyester film (5 mil, 8.5 inch×11inch) was coated with the sample of diluted ink suspension obtained inthe previous step by drawing down a thin ink film on the Clear polyestersurface using Meyer Coating Rod #26. The wet ink film obtained wasallowed to sit on a flat surface for 10 min at room temperature.

The ink film on Clear polyester thus obtained in the previous step wasfurther dried under vacuum at 100° C. for 20 min in a vacuum oven andthen cooled to room temperature to obtain Ink-coated Clear Polyesterfilm.

Square sections (1 inch×1 inch) of the Ink-coated Clear polyester filmthus obtained in the previous step and referred to as Ink Strips werecut out and used to perform ink adhesion tests on primed substrates.

Example 7 Method 2 Preparation of Primed Clear Polyester Substrate Films

Primer coating formulations containing single polymer or combination ofpolymers used as primers were prepared either as clear solutions (30%Solids, in Acetone, MEK, Ethanol, Reagent Alcohol, IPA or water) or asdispersions (30% Solids, in water).

Primer coating formulations thus obtained in the previous step wereapplied on non-Corona treated surface of Clear Polyester films (5 mil,8.5 inch×flinch) and a thin uniform film of Primer coating formulationwas drawn on the Clear Polyester using Meyer Coating Rods #6, #3 or #0to adjust for required dry coat weight (1-2 g/m²).

The primer coated Clear Polyester films thus obtained in the previousstep were either allowed to air-dry for 1 hour at room temperature (forvolatile solvents like Acetone, MEK, Ethanol, Reagent Alcohol or IPA) ordried under vacuum at 130° C. for 15 min in a vacuum oven (for watersolutions or dispersions) to obtain dry primed substrate films.

Rectangular sections (2 inch×6 inch) of dry primed substrate films thusobtained in the previous step and are referred to as Substrate Stripswere cut out and used to perform ink adhesion tests.

Example 8 Method 3 Ink Adhesion Test on Substrate Strips and AdhesionPerformance Grading

The top face of a hot plate (10.5 inch×10.5 inch) was covered with aTeflon sheet (8 inch×8 inch) and the hot plate surface was maintained ata temperature of 120° C. (±4° C.). Sufficient time was allowed for theTeflon sheet to equilibrate with the hot plate surface temperature andtemperature on exposed surface of Teflon sheet was measured using anInfrared thermometer.

The Ink Strip was placed on the heated Teflon sheet with the ink-coatedside facing up. Ink coating on the Ink Strip was allowed to equilibrateto the temperature of the hot plate (120° C.±4° C.) for 2 minutes andtemperature of top ink layer measured using an Infrared thermometer.

The Substrate Strip was placed on the heated Ink Strip with the primedside facing down and in contact with the heated ink coating on the InkStrip.

The Substrate Strip was pressed against the Ink Strip on the hot plateusing a Teflon coated rolling pin while applying maximum possible manualpressure (32 rolls, 1 roll=1 forward roll+1 backward roll) to obtain aSubstrate Strip-Ink Strip assembly.

The Substrate Strip-Ink Strip assembly thus obtained in the previousstep was lifted from the Teflon sheet on the hot plate and placed on acold flat surface with the primed surface of the Substrate Strip facingup and allowed to equilibrate room temperature for 2 min.

After 2 min, the clear polyester backing of the ink strip was manuallyseparated from the Substrate Strip-Ink Strip assembly to leave a thin(˜0.2 mil) layer of ink on the primed surface of Substrate Strip,henceforth referred to as Ink Patch.

A hatch-pattern consisting of 40 small rectangles was scored on inkpatch thus obtained in the previous step using a razor blade.

Office tape (Scotch® Transparent Tape) was applied on the hatch-patternon the ink patch on the primed substrate and firm pressure was appliedon the tape to ensure maximum adhesion of office tape with ink surface.The office tape was allowed to stay on the ink patch for 10 min and thensharply lifted off to check ink removal from the ink patch.

The results from Test Method 1 in this Ink Adhesion Performance Gradingexperiment are as follows:

-   ink removal=0%, Grade=10;-   ink removal=100%, Grade=0.

Example 9 Using Test Method 3

Grade % of with INGREDIENT PHYSICAL Ingredient Office INGREDIENT TYPESTATE in Coating Tape Vp/VA/AcAc Inventive Film 100 7-8 (58.5/40/1.5)Adhesive Ex. 1 Vp/VA/AcAc Inventive Film 100 8-9 (55/40/5) Adhesive Ex.2 VCap/VA/AcAc Inventive Film 100 8-9 (58.5/40/1.5) Adhesive Ex. 3VCap/VA/AcAc Inventive Film 100 8-9 (55/40/5) Adhesive Ex. 4

While a number of embodiments of this invention have been represented,it was apparent that the basic construction can be altered to provideother embodiments that utilize the invention without departing from thespirit and scope of the invention. All such modifications and variationsare intended to be included within the scope of the invention as definedin the appended claims rather than the specific embodiments that havebeen presented by way of example.

We claim:
 1. A coating composition for forming a toner receptive coatingon a substrate containing a polymer comprising: (a) a N-vinyl amidemonomer, (b) a vinyl acetate monomer, (c) a reactive monomer comprisingan acetoacetate moiety, and (d) a solvent.
 2. The coating compositionaccording to claim 1, wherein (a) the N-vinyl amide monomer is selectedfrom the group consisting of N-vinyl pyrrolidone, N-vinyl valerolactam,N-vinyl caprolactam, hydroxyethylpyrrolidone methacrylate, and N-vinylformamide.
 3. The coating composition according to claim 1, wherein (a)and (b) are N-vinyl pyrrolidone-co-vinyl acetate or n-vinylcaprolactam-co-vinyl acetate.
 4. The coating composition according toclaim 3, wherein (a) and (b) is Collacral® VAL.
 5. The coatingcomposition according to claim 1, wherein the monomer in (c) thereactive monomer comprising an acetoacetate moiety is selected from thegroup consisting of amide, alkyl, carboxyl, carbonyl, and ether groups.6. The coating composition according to claim 5, wherein (c) thereactive monomer comprising an acetoacetate moiety is selected from thegroup consisting of acetoacetoxyethyl methacrylate, acetoacetoxyethylacrylate, and allyl acetoacetate.
 7. The coating composition accordingto claim 1, wherein (a) is 0.1-80%, (b) is 1-80%, (c) is 1-80%, and (d)is to 100%, by weight.
 8. The coating composition according to claim 1,having a solids content of about 15-50% and a viscosity of about200-3000 cps.
 9. The coating composition according to claim 1, whereinthe polymer comprising: (a) a N-vinyl amide monomer, (b) a vinyl acetatemonomer, (c) a reactive monomer comprising an acetoacetate moiety, and(d) a solvent is selected from the group consisting of vinylpyrrolidone/vinyl acetate/acetoacetoxyethyl methacrylate, vinylcaprolactam/vinyl acetate/acetoacetoxyethyl methacrylate, vinylpyrrolidone/vinyl acetate/allyl acetoacetate, and vinylcaprolactam/vinyl acetate/allyl acetoacetate.
 10. The coatingcomposition according to claim 1, further comprising (e) a non-reactivehydrophobic monomer.
 11. The coating composition according to claim 10,wherein (e) the non-reactive hydrophobic monomer comprises anon-reactive C₁-C₂₀ alkyl acrylate monomer.
 12. The coating compositionaccording to claim 11, wherein (e) the non-reactive C₁-C₂₀ alkylacrylate monomer is selected from the group consisting of stearylacrylate, butyl acrylate, octyl acrylate, decyl acrylate, and lauryl(meth)acrylate.
 13. The coating composition according to claim 1,further comprising (f) a binder, (g) a pigment, and (h) a surfactant.14. The coating composition according to claim 10, wherein the polymeris selected from the group consisting of vinyl caprolactam/vinylacetate/acetoacetoxyethyl methacrylate/stearyl acrylate and vinylcaprolactam/vinyl acetate/allyl acetoacetoacetate/stearyl acrylate. 15.The coating composition according to claim 1, wherein the composition isin the form of an aqueous dispersion.
 16. The coating compositionaccording to claim 1, wherein the polymer further comprises an additiveselected from the group consisting of adhesives, aerosols, agriculturalagents, anti-soil redeposition agents, batteries agents, beverages,biocides, block copolymers, branch/comb copolymers, cementing agents,cleaning agents, coating agents, conductive materials, cosmetic agents,cross-linkers, dental agents, decorated pigments, detergents,dispersants, drugs, electronics, encapsulations, foods, hair sprays,household-industrial-institutional, inks and coatings, interlaminateadhesives, lithographic solutions, membrane additive agents, metalworking fluids, oilfield agents, paints, paper, paper sizing agents,personal care agents, pharmaceuticals, pigment additives, plasters,plastics, printing, reactive biocides, reactive rheology modifiers,refractive index modifiers, sequestrants, soil release agents, staticcontrol agents, and wood-care agents.
 17. The coating compositionaccording to claim 10, wherein the polymer further comprises an additiveselected from the group consisting of adhesives, aerosols, agriculturalagents, anti-soil redeposition agents, batteries agents, beverages,biocides, block copolymers, branch/comb copolymers, cementing agents,cleaning agents, coating agents, conductive materials, cosmetic agents,cross-linkers, dental agents, decorated pigments, detergents,dispersants, drugs, electronics, encapsulations, foods, hair sprays,household-industrial-institutional, inks and coatings, interlaminateadhesives, lithographic solutions, membrane additive agents, metalworking fluids, oilfield agents, paints, paper, paper sizing agents,personal care agents, pharmaceuticals, pigment additives, plasters,plastics, printing, reactive biocides, reactive rheology modifiers,refractive index modifiers, sequestrants, soil release agents, staticcontrol agents, and wood-care agents.
 18. A toner substrate coated witha coating composition containing a polymer comprising: a polymercomprising: (a) a N-vinyl amide monomer, (b) a vinyl acetate monomer,(c) a reactive monomer comprising an acetoacetate moiety, and (d) asolvent.
 19. The toner substrate coated with a coating compositionaccording to claim 18, further comprising (e) a non-reactive hydrophobicmonomer.
 20. A flexible food package substrate coated with a coatingcomposition containing a polymer comprising: (a) a N-vinyl amidemonomer, (b) a vinyl acetate monomer, (c) a reactive monomer comprisingan acetoacetate moiety, and (d) a solvent.
 21. A flexible food packagesubstrate coated with a coating composition according to claim 20,further comprising (e) a non-reactive hydrophobic monomer.